CN103505983B - For capturing the capture block being made up of the elementary sulfur deposited on porous support of heavy metal - Google Patents

For capturing the capture block being made up of the elementary sulfur deposited on porous support of heavy metal Download PDF

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CN103505983B
CN103505983B CN201310258592.2A CN201310258592A CN103505983B CN 103505983 B CN103505983 B CN 103505983B CN 201310258592 A CN201310258592 A CN 201310258592A CN 103505983 B CN103505983 B CN 103505983B
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capture block
range
carrier
mercury
porous carrier
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CN103505983A (en
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F.波尔舍龙
K.巴尔特莱
A.博多
M-A.莱利亚
A.尼古洛
T.阿尔马罗利
C.朱班
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IFP Energies Nouvelles IFPEN
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Abstract

The application is related to the capture block being made up of the elementary sulfur deposited on porous support for capturing heavy metal.The present invention relates to remove the heavy metal present in dry or wet gaseous effluent (1) by means of capturing block (2), particularly mercury and possible arsenic and lead, the capture block (2), which includes at least a portion, has the porous carrier of low middle cell size, and the active phase based on sulphur.Present invention advantageously applies to the processing of the gas of industrial source, synthesis gas or natural gas.

Description

For capturing being caught by what the elementary sulfur deposited on porous support formed for heavy metal Obtain block
Technical field
The present invention relates to removed by means of capturing block (capture mass) present in dry or wet gaseous effluent Heavy metal, particularly mercury and possible arsenic and lead, the capture block, which includes at least a portion, has the porous of low middle cell size Carrier, and the active phase based on elementary sulfur.Present invention advantageously applies to the place of the gas of industrial source, synthesis gas or natural gas Reason.
Background technology
Mercury is metal pollutant, its many regional such as Niger bay, South America, north African or Asian-Pacific area in the world Found in caused gaseous state or liquid hydrocarbon.
For several reasons, it is industrial desired that mercury is removed from hydrocarbon-fraction (cut)：
The safety of operating personnel, because element mercury is volatile and serious nerve is shown due to suction The danger of poisoning, and the organic form of mercury shows similar danger due to skin contact；
And for the reason for prevent the heterogeneous catalyst inactivation for making the upgrading of this kind of liquid hydrocarbon fraction.Due to mercury Qi Hua, mercury cause to deposit the nanoparticles sinter of noble metal such as platinum or palladium on porous support, and the porous carrier is used for Various catalytic reactions for example pass through the selective hydration of alkene caused by the steam pyrolysis or catalytic pyrolysis of liquid hydrocarbon.Catalyst A large amount of reductions of specific surface area of component metals particle cause the loss of its catalytic activity highly significant.
Industrially, the guard bed (guard bed) of capture block is filled with by cycling through pending effluent And carry out removing mercury from liquid or fraction of gaseous hydrocarbons.The reaction is specific, is caught so as to then pending impurity is retained in Obtain in the surface of block or on surface, and the effluent therefore discharged from the bed of capture block is purified.
The capture of heavy metal such as mercury can be easily by making mercury be carried out with active sulfur-base phase reaction.Document US 7 645 306 B2 show：According to following formula, element mercury (Hgo) in an irreversible fashion reduce copper sulfide CuS：
Hgo + 2 CuS → Cu2S + HgS。
The product HgS of formation, it is known that cinnabar or metacinnabarite, there is the chemical inertness within the scope of wide temperature and be The special characteristic of solid.Mercury thus captures in the bed of capture block and pending effluent is purified.Vulcanized based on metal Thing these capture blocks generally for example by initially make oxide precursor such as CuO deposit, then by application vulcanisation step with Metal oxide is transformed into metal sulfide and prepared.
It is mutually possible directly using the activity being made up of elementary sulfur to remove the vulcanisation step.In fact, with as follows Irreversibly, elementary sulfur S and element mercury HgoReaction：
Hg° + S → HgS (1)
Reacting (1) is spontaneous and has negative free energy Δ G in wide temperature range, usual 0 DEG C -150 DEG C (kJ/mole)。
Traditionally, the capture block based on elementary sulfur is obtained by the method for elementary sulfur to be immersed on active carbon type carrier .As example, document US 4 708 853 describes the method for synthesizing capture block, and solid state component is made during this method Sulphur is contacted and mixed with activated carbon granule, is then heated above the temperature of about T=150 DEG C up to 10-90 minutes so that sulphur Liquefaction.Then liquid sulfur moves to the porous texture (vein) of activated carbon and is then quenched solid, so that sulfur curable.
Activated carbon has cheap special characteristic, and the cost for therefore producing capture block is low.However, this kind of porous carrier Operationally run into many shortcomings.
First, activated carbon be typically derived from from food industry (such as：Cocoanut shell) or from energy field (such as：Matchmaker, Jiao Charcoal) obtain residue, and therefore have can be with widely varied and unmanageable porosity.Therefore, almost systematically, it will Comprising the porosity for being referred to as micropore (definition provided in such as IUPAC names), that is, have the hole size no more than 2 nm (i.e. straight Footpath d).The presence of this some holes have impact on capture block guard bed performance, in this sense for, mercury spreads in this some holes It is unfavorable.Therefore, mercury, which takes more time, reaches avtive spot and along with fixed time of contact, finds capture effect Rate reduces.
In addition, pending effluent generally comprises the water content of non-zero.Caused in the presence of pending gas reclaimed water The phenomenon condensed on the porous carrier used, this is known as capillary condensation.At a given temperature, in the saturation steaming less than water Under the pressure of vapour pressure (P0), the phenomenon causes the appearance of aqueous water.For the model hole with cylinder, Kelvin side can be used Journey (equation 2) determines critical pore radius (Rc), and when beyond the aperture, hole will be filled by aqueous water.
Rc = -2γVmcosθ/RT/log10(P/P0) (2)
Wherein P is gas pressure, and T is gas temperature, and R is ideal gas constant (R=8.314 J/K/mole), VmFor The molal volume of water, γ is air/water surface tension, and θ is water/solid contact angle.P/P0 corresponds to the relatively wet of effluent The definition of degree.Therefore for capillary condensation phenomenon, particularly less hole, micropore (d<2 nm) than mesopore (2< d < 50 ) or macropore (d nm>50 nm) it is much sensitive.
Capillary condensation mechanism may also occur along with hydrocarbon steam or VOC.
The presence of capillary condensation has main influence for the function of capturing block, because it is caused for material in bed There is high resistance in transfer, and prevents mercury from acquiring up to the path of whole active phase.Then fairly frequently, the property of guard bed It can significantly change.During the overnight functional performance of guard bed, it has been observed that the performance of the sulfur type capture block on activated carbon Decline.The dysfunction is attributed to the temperature reduction in night reactor, and this is related to occurring capillary condensation in bed.It is similar Ground, it has been shown that for the model gas (mercury in nitrogen) with 10% relative humidity, based on the sulphur deposited on the activated carbon Capturing the performance of block reduces by 25% (Mc Namara, J.D. ＆ Wagner, N.J., Process effects on activated carbon performances and analytical methods used for low level mercury removal in natural gas applications, Gas Sep. Purif. 10(2) 1996,137- 140)。
The problem of moisture-proof, is therefore, it is intended that effluent must reheat or water must condense in the following manner：Make The upstream cooling of guard bed-this produces high running cost, or mercury guard bed is placed on for water to be removed from air-flow The downstream of industrial drying machine.However, those drying devices dissolve in diol type compound therein usually using mercury.Document WO 2005/047438 especially shows that the concentration of mercury in glycol can reach the high numerical value of 2.9 ppm ranks.In the regeneration step phase Between, glycol solution is heated to the temperature close to T=200 DEG C, and then a part of mercury emissions into air.
In addition, the capture block based on deposition sulphur on the activated carbon is generally subjected to asking for stability in humid conditions very much Topic, because in the presence of water or liquid hydrocarbon, activity may be mutually entrained.It is existing weak between active phase and activated carbon surface Related characteristic of the solubility of sulphur in energy interaction and this medium, under causing the service life for capturing block violent Drop.
Document EP 0 107 582 describes the capture block based on the sulphur on the porous carrier formed by aluminum oxide.It is described Porous carrier includes the high pore volume in the range of 10-100 nm.However, the capture block pair described in document EP 0 107 582 In active mutually sensitive by the phenomenon of pending fluid carry-over；The phenomenon also is known as leaching (leaching).
The content of the invention
The present invention proposes the capture block being made up of the elementary sulfur deposited on the alumina support, and the capture block resists capillary Condense the phenomenon mutually carried secretly with activity.
Generally speaking, the present invention describes capture block for capturing mercury, described piece comprising deposition on porous support Active phase, the activity mutually include elementary sulfur, and the porous carrier has pore volume V0.004>0.1 mL/g, V0.004Correspond to With less than 0.004 μm, i.e. the cumulative volume in the hole of the size less than 4 nm.
According to the present invention, the porous carrier can be made up of at least one of following oxide：Aluminum oxide, titanium oxide, Zirconium oxide and silica.Preferably, porous carrier is made up of aluminum oxide.
The porous carrier can have 0.3-1 cm3Total pore volume in/g range, the porous carrier can have 100-400 m2BET specific surface area in/g range, and the porous carrier can be included with Na2The 10- of O weight meters The sodium of amount in the range of 5000 ppm.
The porous carrier can have pore volume V0.002<0.002 mL/g, V0.002Corresponding to less than 0.002 μm, i.e. the cumulative volume in the hole of 2 nm size.
The porous carrier can have pore volume V0.1>0.2 mL/g, V0.1Corresponding to less than 0.1 μm, i.e., The cumulative volume in the hole of 100 nm size.
The porous carrier can have pore volume V0.1-0.01<0.15 mL/g, V0.1-0.01Corresponding to 0.1 μ In m-0.01 μ ms, i.e., the cumulative volume in the hole of the size in the range of 100-10 nm.
The activity mutually can include elementary sulfur Sx, x is in the range of 1-30.
Relative to the weight of the capture block, amount in terms of the weight of elementary sulfur can in the range of 1%-60%, and Relative to the weight of the capture block, the amount in terms of the weight of porous carrier can be in the range of 40%-99%.
The capture block of the present invention can be by making sulphur deposition prepare on porous support., can be by following as example Mode deposits sulphur：By making sulfur powder be contacted with carrier, either by making sulfur vapor be contacted with carrier or by making liquid Sulphur in solution contacts with carrier, and step then is dried by heating the carrier of sulfur-bearing.
The invention further relates to the method for removing the mercury included in gaseous effluent, wherein making gaseous effluent and according to this hair Bright capture block contact.
Before contact, operation can be dried to reduce the relative humidity of gaseous effluent.The drying process can be with Carry out in the following manner：Contacted by means of the sieve with water-absorption, by means of being contacted with the absorbent solution comprising glycol, or Person passes through heated gaseous effluent.
The contact can at a temperature in the range of -50 DEG C to 115 DEG C and 0.1 bar of absolute pressure to 200 bars definitely Under pressure in pressure limit, and with 50-50000 h-1In the range of space time velocity carry out.
In the variant of the inventive method, the relative humidity of gaseous effluent can be in the range of 60%-100%.
Gaseous effluent can be selected from：Burning cigarette, synthesis gas, natural gas and hydrocarbon effluent.
In surprise, the inventors have discovered that：Using according to the present invention, based on be dispersed at least a portion have it is low The capture block of elementary sulfur on the porous carrier of middle cell size, improved heavy metal adsorption performance can be obtained, especially for mercury Speech.The function of the capture block of the present invention will not actually be changed by the presence of water vapour in gas, or even in high hygroscopicity water It is also such under flat.In all methods for handling dry or wet gaseous effluent, weight present in these chargings is being removed In metal, particularly mercury, the use of capture block of the invention is of crucial importance；The example that can also be quoted is arsenic and lead.
Brief description of the drawings
Further features and advantages of the present invention will become obvious from the following description carried out referring to the drawings, wherein：
Fig. 1 is the schematic diagram for being used to capture the method for mercury according to the present invention；
Fig. 2 represents the variant of the inventive method；
Fig. 3 represents to have captured the difraction spectrum of the capture block according to the present invention of mercury.
Embodiment
In this manual, under IUPAC rules, term " micropore ", which refers to have, is less than 2 nm, i.e. 0.002 μm straight The hole in footpath；Term " mesopore ", which refers to have, is more than 2 nm, i.e., 0.002 μm and is less than 50 nm, i.e., 0.05 μm of diameter Hole, and term " macropore " refer to have be more than 50 nm, i.e., the hole of 0.05 μm of diameter.
The present invention relates to the formula of the capture block for capturing the heavy metal included in gaseous feed, particularly mercury.Institute State the active phase composition that capture block forms by porous carrier and by elementary sulfur.Active mutually deposition is on porous support.
Preferably, sulphur relative to capture block weight weight ratio in the range of 1%-60%, preferably 2%-40%'s In the range of and very preferably in the range of 2%-15%, or the model even in the range of 2%-10% or in 4%-10% In enclosing.
Preferably, porous carrier is in the range of 40%-99% relative to the weight ratio of the weight of capture block, is preferably existed In the range of 60%-98% and very preferably in the range of 90%-98%.
It is active to be mutually made up of elementary sulfur, the i.e. sulfur molecule not with another compound chemical bonding.Active can be mutually member Plain sulphur Sx, x is in the range of 1-30, and preferably in the range of 4-20 and very preferably equal to 8,7,6,12 or 18, this is right Should be in the most stable of allotropic form of elementary sulfur.The elementary sulfur of composition capture block for itself and heavy metal, particularly with Mercury reaction performance and be chosen.
The composition of porous carrier can be selected from aluminum oxide, silica, zirconium oxide, titanium oxide or above-cited oxide Any kind of mixture.According to the present invention, carrier is preferably made up of Woelm Alumina.Preferably, the carrier substantially by Aluminum oxide is individually composed, i.e., relative to the weight of carrier, carrier includes at least 95 weight %, or even 98 weight % or even 99 Weight % aluminum oxide.
The feature of the porous carrier of the present invention capture block referred in this manual corresponds to has been deposited on load in sulphur The feature of carrier before on body.
In the case of porous carrier is aluminum oxide, alumina support can by various methods known to technical staff, Such as synthesized by following methods.
The first supported synthesis methods：Carry out three hydroxides for example obtained by the method for being commonly known as Bayer methods Aluminium (Al (OH)3) type (also being known as gibbsite or gibbsite) precursor fast dewatering.Then, such as by being granulated carry out Shaping, followed byOptionalHydro-thermal process,ThenCalcining so that aluminum oxide is made.This method specifically in P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, J.L. Le Loarer, J.P. Jolivet, C. Froidefond, Alumina, Handbook of Porous Solids, F. Schüth, K.S.W. Sing, J. Weitkamp writes, Wiley-VCH, Weinheim, Germany, and 2002, it is described in detail in the 1591-1677 pages of document. This method can be used for the aluminum oxide for preparing commonly known as flash distillation aluminum oxide (flash alumina).
Second of supported synthesis methods：Produced by with 150-600 m2The γ of high-specific surface area in/g range- (hydroxide) oxygen aluminium profiles (AlO (OH)) also is known as boehmite) precursor composition gel method.Then, such as by mixed Close-it is extruded into gel.Then, a series of heat treatment or optional hydro-thermal process are carried out on product so that oxidation is made Aluminium.Boehmite gel can for example by alkalescence and/or acid aluminium salt solution precipitation obtain, it is described precipitation by change pH or Any other method known to person technical staff causes.This method is specifically in P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, J.L. Le Loarer, J.P. Jolivet, C. Froidefond, Alumina, Handbook of Porous Solids, F. Sch ü th, K.S.W. Sing, J. Weitkamp write, Wiley- VCH, Weinheim, Germany, 2002, described in the 1591-1677 pages of document.
Preferably, first method is carried out to obtain the porous alumina carrier for present invention capture block.Very preferably Ground, described first method is carried out in the case of without any hydro-thermal process, so that with 0.002-0.004 μm In the range of diameter number of perforations maximize.Then the preparation of capture block of the invention comprises the following steps：
A) the three aluminium hydroxides (Al (OH) for example obtained by the method for being commonly known as Bayer methods3) type (also is known as Gibbsite or gibbsite) precursor fast dewatering；
B) for example shape aluminum oxide by granulation；
C) calcinated support at 250 DEG C -600 DEG C.
According to the present invention, the porous carrier has pore volume V0.004>0.1 mL/g, V0.004Corresponding to less than The cumulative volume in the hole of 0.004 μm of size.The hole size corresponds to the diameter in the preferable theoretical hole for being assumed to be cylinder. Preferably, selection has pore volume V0.004>0.12 mL/g porous carrier.
In addition, hole carrier preferably has pore volume V0.01>0.2 mL/g, V0.01Corresponding to the chi with less than 0.01 μm The cumulative volume in very little hole.The hole size corresponds to the diameter in the preferable theoretical hole for being assumed to be cylinder.Preferably, selection tool There is pore volume V0.01> 0.025 mL/g；More preferably V0.01>0.28 mL/g porous carrier.
With high pore volume V0.004, such as V0.004>0.06 mL/g and optionally pore volume V0.01>0.2 mL/g, The fact that small mesopore be present means that enough sulphur can be limited in hole so that it is proper using capture block when its not by Effluent is carried secretly, i.e., avoids the phenomenon of leaching sulphur completely.
According to the present invention, porous carrier preferably has the low pore volume being made up of big mesopore and macropore：V0.1-0.01 < 0.15 mL/g, V0.1-0.01Corresponding to the cumulative volume in the hole with the size in 0.1 μm of -0.01 μ m.The hole size Corresponding to the diameter in the preferable theoretical hole for being assumed to be cylinder.Preferably, selection has pore volume V0.1-0.01 < 0.12 mL/ g；It is highly preferred that V0.1-0.01<0.11 mL/g porous carrier.
With limited pore volume V0.1-0.01, such as V0.1-0.01<0.15 mL/g and optionally pore volume V0.01 > 0.2 ML/g, i.e., the fact that big mesopore and macropore on a small quantity be present means that the entrainment for the sulphur being deposited in this some holes, institute can be limited State entrainment and be attributed to the effluent used during capture block.
Volume V0.01And V0.1-0.01Mercury Porosimeter [Rouquerol F. can be passed through; Rouqerol J.; Singh K. Adsorption by powders & porous solids: Principle, methodology and Applications, Academic Press, 1999] measurement.
Pore volume V0.004It can be measured using following methods：
The total pore volume (TPV) of 1/measure:Using mercury Porosimeter measurement grain density (Dg), and surveyed using helium Densimeter measurement absolute density (Dab), then calculated TPV (mL/g) as 1/Dg -1/Dab；
2/pass through mercury Porosimeter (VHg) [Rouquerol F.; Rouqerol J.; Singh K. Adsorption by powders & porous solids: Principle, methodology and Applications, Academic Press, 1999] measure pore volume；
3 / V0.004 = TPV – VHg。
According to the present invention, porous carrier has micro pore volume V0.002<0.002 mL/g, preferably V0.002 < 0.001 ML/g and more preferably V0.002For 0.V0.002Corresponding to the accumulation body in the hole (i.e. micropore) of the size with less than 0.002 μm Product.The hole size corresponds to the diameter for the preferable theoretical pore for being assumed to be cylinder.
Low V0.002Pore volume and high V0.004Pore volume means there is 0.002 μm of -0.004 μ m interior diameter The cumulative volume of small mesopore can maximize.Therefore, active sulfur present in these small mesopores of present invention capture block Site is accessible to for the mercury contained in pending charging, it means that capture block can be captured effectively Mercury, while avoid when using effluent entrainment sulphur when capturing block.
Pore volume V0.002Can be by applied to by N2T-plot methods [the Rouquerol for the data that Porosimeter obtains F.; Rouqerol J.; Singh K. Adsorption by powders & porous solids: Principle, Methodology and applications, Academic Press, 1999] measurement.
Advantageously, porous carrier has in 0.3-1 cm3In/g range, preferably in 0.4-0.7 cm3It is total in/g range Pore volume.
The specific surface area of the porous carrier of the capture block according to the present invention determined by BET method is advantageously in 100-400 m2In the range of/g, preferably in 150-370 m2In the range of/g, more preferably in 200-370 m2In the range of/g, still more It is preferred that in 250-370 m2In the range of/g.
Carrier for the capture block of the present invention can be included with Na2O weight meters in the range of 10-5000 ppm The sodium of amount, the preferably amount in the range of 100-5000 ppm, or the amount even in the range of 1000-5000 ppm.
Porous carrier and thus obtained capture block of the invention can be the form of multiple element, and every kind of element has pearl The shape for any other geometry that grain, cylindrical, leafy extrudate, wheel, hollow cylindrical or technical staff use. Forming each element of capture block has the feature of capture block of the present invention.It is highly preferred that porous carrier and thus obtained The capture block of invention has in the range of 0.4-100 mm to be multiple, preferably in the range of 0.5-50 mm, more preferably exists The bead form of diameter in the range of 0.5-10 mm.
Porous carrier can use any method known to technical staff to shape.As example, following shaping can be used Method：Fluid bed granulation, high-rate of shear mixer/granulation machine, rotation drum, mixing/extrusion, or it is round as a ball (spheronization)。
According to the present invention capture block can by technical staff known to following synthesis path, by making Elemental sulfur deposition Prepared on above-mentioned porous carrier.As example, can use be described in patent US 4 500 327 and US 4 708 853 Following scheme, or following proposal.
For making the first scheme of Elemental sulfur deposition on porous support be formed by following the steps below：
A) hybrid solid element sulfur powder and porous carrier；
B) mixture is heated in atmosphere under the temperature T in the range of 110 DEG C -220 DEG C, continues 1h-50h models Enclose the interior time；
C) mixture band is back to environment temperature.
For making the alternative plan of Elemental sulfur deposition on porous support be formed by following the steps below：
A) by making porous carrier reach 120 DEG C -175 DEG C, preferably 150 DEG C, with for example distilling to obtain by elementary sulfur Sulfur vapor contact and impregnate；
B) the temperature T heated the mixture in the range of 140 DEG C -160 DEG C, preferably to T=150 DEG C, 90 minutes are continued；
C) the temperature T heated the mixture in the range of 160 DEG C -180 DEG C, preferably to T=170 DEG C, continue again in addition 45 minutes；
D) mixture band is back to environment temperature.
Can for example it be defined below according to whole description prepared by the capture block of the present invention：
A) three aluminium hydroxides (Al (OH)3) type precursor fast dewatering；
B) it is granulated the aluminum oxide obtained from step a)；
C) will be from the porous carrier that step b) is obtained in the range of 250 DEG C -600 DEG C, preferably at 400 DEG C -500 DEG C In the range of, such as calcined under 450 DEG C of T；
D) by making to reach in the range of 120 DEG C -175 DEG C from the porous carrier that step c) is obtained, such as 150 DEG C of temperature T, contacted with the sulfur vapor for distilling to obtain by elementary sulfur to impregnate；
E) mixture obtained from step d) is heated to the temperature T in the range of 140 DEG C -160 DEG C, such as to temperature T =150 DEG C, continue 90 minutes；
F) mixture obtained from step e) is heated to the temperature T in the range of 160 DEG C -180 DEG C, such as to temperature T =170 DEG C, continue 45 minutes again in addition；
G) mixture band is back to environment temperature.
According to the present invention, in order to obtain with pore volume V0.004>0.1 mL/g and there is preferably smaller than 0.15 mL/g Pore volume V0.1-0.01Capture block, directly carry out sulphur after firing and be deposited on step on porous alumina carrier.Preferably, Without hydro-thermal process between the forming step of carrier and calcining step.In fact, the hydro-thermal process will have in the present invention There is undesired opening hole and therefore increase pore volume V0.1-0.01Influence, as patent EP 0 055 164 is instructed.
It is used to capture the heavy metal contained in gaseous effluent, such as mercury, arsenic or lead according to the capture block of the present invention.This hair Bright capture block is very suitable for capturing the mercury contained in gaseous effluent.Such as make the fixed bed form of placement in the reactor Capture block contacted with pending gaseous effluent.
Reference picture 1, the pending gaseous effluent reached by pipeline 1 is introduced to the anti-of the capture block containing the present invention Answer in device 2.Bed 2 includes multiple key elements, and it each has the feature of the capture block of the present invention.In the bed adsorption effluent for capturing block The mercury contained, to obtain the gaseous effluent that mercury exhausts, the effluent is discharged by pipeline 3 from reactor 2.In effluent 3 Concentration of the concentration of mercury less than the mercury of effluent 1.
Referring now to Figure 2, the pending gaseous effluent introducing device 5 that will be reached by pipeline 4, to reduce gaseous flow Go out the relative humidity of thing.Device 5 can be that water captures block, such as the molecular sieve based on zeolite.Device 5 can also carry out glycol The device of method.In this case, gaseous effluent is made to be contacted with the absorbent solution comprising glycol, thus the solution absorbs stream Go out the water contained in thing.As example, the glycol process described in document WO 2005/047438 can be used.Selectively, Device 5 can be heat exchanger, and it can be used for the temperature of gaseous effluent raising such as 3 DEG C -10 DEG C.It will be obtained from device 5 Effluent by pipeline 6 be introduced into comprising according to the present invention capture block bed reactor 7 in.Bed 7 includes multiple key elements, its Each there is the feature of the capture block of the present invention.The mercury contained in the bed adsorption effluent of block is captured, to obtain the gas that mercury exhausts State effluent, the effluent are discharged by pipeline 8 from reactor 7.The concentration of mercury is less than mercury in effluent 4 in effluent 8 Concentration.
The gaseous effluent of the method according to the invention processing can be burning cigarette, synthesis gas or natural gas, or hydrocarbon stream Go out thing, such as gaseous state oil distillate.
Such as the purpose for generating, burning cigarette is burnt in the boiler by hydrocarbon, biogas, coal, or passes through combustion gas wheel Machine produces.These cigarettes, and can be with the temperature of 20 DEG C of -60 DEG C of scopes, the pressure of 1-5 bars of (1 bar=0.1 MPa) scope Comprising the nitrogen in the range of 50%-80%, the carbon dioxide in the range of 5%-40%, the oxygen in the range of 1%-20%, and some are miscellaneous Matter such as SOx and NOx, if they are not removed in downstream by acid stripping method.
Synthesis gas includes carbon monoxide CO, hydrogen H2(usual H2/ CO ratios be equal to 2), water vapour (generally washed At a temperature of be saturation) and carbon dioxide CO2(10% grade).Pressure, but can be high generally in the range of 20-30 bars To 70 bars.It also contains sulfur-containing impurities (H2S, COS etc.), nitrogen-containing impurity (NH3, HCN) and halogenated impurity.
Natural gas is mainly made up of gaseous hydrocarbon, but can be included several in following acid compound：CO2、H2S, sulphur Alcohol, COS, CS2.The amount of these acid compounds can be with widely varied, and for CO2And H240% can be up to for S.My god The temperature of right gas can be in the range of 20 DEG C -100 DEG C.The pressure of pending natural gas can be in 10-120 bars of scope It is interior.
Various forms of heavy metals, such as mercury, arsenic or lead are included according to the pending gaseous effluent of the present invention.As Example, mercury is to be known as Hg0- correspond to the form of element mercury or atomic mercury, with molecular forms, or in the form of an ion for example Hg2+It is found with its complex compound.
Pending gaseous effluent includes the heavy metal of variable proportion.As example, pending gaseous effluent is special It is not mercury/Nm that natural gas flow includes 10 nanograms to 1 gram3Gas.
It is being usually -50 DEG C to 115 DEG C of scope that the capture block of gaseous effluent and the present invention, which can be made, preferably 0 DEG C - At a temperature of 110 DEG C of scope and more preferably 20 DEG C of -100 DEG C of scopes, and in such as 0.1-200 bars of scope, preferably 1- 150 bars of scope and it is highly preferred 10-120 bars in the range of absolute pressure under contact.
Advantageously, when gaseous effluent contacts with capture block, the HSV (space-times that use in the purification process of the invention The volume of speed, i.e. gaseous effluent/capture block product/hour) in 50-50000 h-1In the range of.In the feelings of gas feed In shape, HSV is preferably in 50-500 h-1In the range of.
Pending gaseous effluent can be wet, i.e., it can include the water vapour of change ratio.Gaseous effluent In moisture absorption it is horizontal be preferably 0-100%, more preferably preferably 0-95% and 0-90%.
For the amount of pending charging reclaimed water, capture block of the invention is firm, i.e. even if when pending gas Its non-degradable or only seldom degraded when state effluent has high moisture, and mercury acquisition performance keeps high.According to The present invention, it can handle with 60%-100% relative humidity, or even 70%-95%, and up to 80% to 95% is relatively wet The wet gaseous effluent of degree.
Embodiments illustrated below is used for the function and advantage of the example present invention.
Embodiment A:According to the capture block M of the present invention1Preparation
Capture block M1Prepared using the mixture of alumina beads and the elementary sulfur of solid powdery.
The description of carrier:
Carrier is by being granulated the flash distillation aluminum oxide prepared, having the feature referred in table 1：
Numerical value
Na2O (ppm) 3450
BET surface areas (m2/g) 321
V0.004 (mL/g) 0.14
V0.002 (mL/g) 0
V0.01 (mL/g) 0.30
V0.1-0.01 (mL/g) 0.10
TPV* (mL/g) 0.46
WTV** (mL/g) 0.4
Table 1
* TPV=total pore volume.
TPV is determined using following calculate：Densimeter is surveyed using mercury Porosimeter measurement grain density (Dg), and using helium Absolute density (Dab) is measured, is then calculated TPV (mL/g) as 1/Dg -1/Dab.
* WTV=water absorbent product
WTV is determined by experiment：
10 g aluminum oxide are put into pan-type pelletizer；
The filling of graduated buret has been previously heated to 40 DEG C of liquor potassic permanganate；
Impregnated dropwise on the bead rotated in pan-type pelletizer, until there is uniform purple (maximum time =20 min).
Capture the preparation of block：
Capture block M1Prepare in the following manner：Elementary sulfur is set to be contacted with carrier.By mixture in atmosphere in T=110 DEG C 10 h of lower heating, are subsequently cooled to environment temperature.
Embodiment B:According to the capture block M of the present invention2Preparation
Capture block M2Prepared by using the dry oxide impregnation aluminium pill grain of the solution comprising sulphur emulsion.
The description of carrier：
Carrier is by being granulated the flash distillation aluminum oxide prepared, having the feature referred in table 2：
Numerical value
Na2O (ppm) 3450
BET surface area (m2/g) 321
V0.004 (mL/g) 0.14
V0.002 (mL/g) 0
V0.01 (mL/g) 0.30
V0.1-0.01 (mL/g) 0.10
TPV (mL/g) 0.46
WTV (mL/g) 0.4
Table 2.
The preparation of solution：
Solution is prepared in the following manner：The emulsion form 60 g sulphur being mixed into water, to obtain volume equal to 240 ML solution, accumulated corresponding to the water absorbent of 600 g carriers.
Capture the preparation of block：
Capture block M2Prepared by using the above-mentioned solution of 240 mL and the dry dipping of the above-mentioned alumina beads of 600 g.
Then the bead of dipping is dried at 90 DEG C in the air stream.
Embodiment C:Capture block M3Preparation (contrast)
Capture block M3Prepared by using the dry oxide impregnation aluminium pill grain of the solution comprising sulphur emulsion.
The description of carrier：
Carrier is by being granulated the flash distillation aluminum oxide prepared, having the feature referred in table 3：
Numerical value
Na2O (ppm) 300
BET surface area (m2/g) 153
V0.004 (mL/g) 0.03
V0.002 (mL/g) 0
V0.01 (mL/g) 0.18
V0.1-0.01 (mL/g) 0.23
TPV (mL/g) 0.91
WTV (mL/g) 0.72
Table 3.
The preparation of solution：
Solution is prepared in the following manner：The emulsion form 45 g sulphur being micronized being mixed into water, to obtain volume Equal to 432 mL solution, accumulated corresponding to the water absorbent of 600 g carriers.
Capture the preparation of block：
Capture block M3By making the above-mentioned solution of 432 mL be contacted with the above-mentioned alumina beads of 600 g, made by dry dipping It is standby.
Then the bead of dipping is dried at 90 DEG C in the air stream.
Embodiment D:Capture block M4Preparation (contrast)
Capture block M4Prepared by using the dry oxide impregnation aluminium pill grain of the solution comprising sulphur emulsion.
The description of carrier：
Carrier is by being granulated the flash distillation aluminum oxide prepared.
Numerical value
Na2O (ppm) 320
BET surface area (m2/g) 198
V0.004 (mL/g) 0.05
V0.002 (mL/g) 0
V0.01 (mL/g) 0.33
V0.1-0.01 (mL/g) 0.31
TPV (mL/g) 0.70
WTV (mL/g) 0.55
Table 4.
The preparation of solution：
Solution is prepared in the following manner：The emulsion form 45 g sulphur being mixed into water, to obtain volume equal to 330 ML solution, accumulated corresponding to the water absorbent of 600 g carriers.
Capture the preparation of block：
Capture block M4By making the above-mentioned solution of 330 mL be contacted with the above-mentioned alumina beads of 600 g, made by dry dipping It is standby.
Then the bead of dipping is dried at 90 DEG C in the air stream.
Embodiment E:Capture block M5Preparation (contrast, according to document EP 0 107 582)
Capture block M5Prepared by using the dry oxide impregnation aluminium pill grain of the solution comprising sulphur emulsion.
The description of carrier：
Carrier be by be granulated prepare flash distillation aluminum oxide, before the carrier calcine at 800 DEG C, comprising nitric acid with Carried out in the water-bearing media of acetic acid at 150 DEG C under vapor phase processing 15 hours (referring to the scheme in patent FR 2 496 631, It is used to prepare the capture block being claimed in patent EP 0 107 582).
Numerical value
Na2O (ppm) 565
BET surface area (m2/g) 132
V0.004 (mL/g) 0.01
V0.002 (mL/g) 0
V0.01 (mL/g) 0.03
V0.1-0.01 (mL/g) 0.71
TPV (mL/g) 1.01
WTV (mL/g) 0.95
Table 4。
The preparation of solution：
Solution is prepared in the following manner：The emulsion form 45 g sulphur being mixed into water, to obtain volume equal to 330 ML solution, accumulated corresponding to the water absorbent of 600 g carriers.
Capture the preparation of block：
Capture block M5By making the above-mentioned solution of 330 mL be contacted with the above-mentioned alumina beads of 600 g, made by dry dipping It is standby.
Then the bead of dipping is dried at 90 DEG C in the air stream.
Embodiment F:Capture the remaining loss test of the active phase of block
For the ratio of each capture block, first evaluation " extractible " active phase.Therefore, adsorbent volume will be corresponded to (Vm = 3 cm3) the quality of research be mmCapture block set with fixed-bed structure.Make gaseous nitrogen stream with 300 NL/h's The pressure of flow rate, 70 DEG C of temperature and 20 MPa passes through adsorbent bed.
After 3 days, solid is removed from fixed bed reactors, then weigh (ms).Then record relative to being initially present in Capture the quality of the active phase on block, the mass change of each capture block obtained, Δ m=mm – ms, it is as follows：
ΔS = (Δm x 100) / (%S x mm / 100)
It is derived from the percent delta S of active phase that can be extracted during heavy metal capture operation from carrier.As a result It is recorded in table 5.
Quality ΔS/%
M1 0
M2 0
M3 3
M4 20
M5 40
Table 5.
The result illustrates more preferable suppression of the capture block of the present invention to active mutually loss.
Embodiment G:In capture block M in dried medium1、M2、M3And M4On mercury adsorption capacity experiment
The mercury adsorption features of capture block produced above are tested in the reactor.Capture block is put into fixed bed reactors In.By volume Vm = 3 cm3Adsorbent prepared with fixed-bed structure.Make comprising charging, [Hg]e = 1060 µg/Nm3Mercury Gaseous nitrogen stream passes through adsorbent bed with the pressure of 300 NL/h flow rate, 70 DEG C of temperature and 20 MPa.Use is with original The specific in-line analyzer of mercury of sub- fluorescence principle work, in the concentration of reactor inlet and outlet measurement mercury.
These operating conditions are used for each capture block sample until its saturation.Mercury at the entrance and exit of reactor is dense When degree is strictly equal, it is believed that mercury captures block saturation.
Then by producing the material balance of mercury, Ke Yiping between inner reaction device entrance during the whole test and outlet Valency becomes irreversibly mercury [Hg] of the chemical absorbing on each capture blockfConcentration.The mercury saturation of each capture block sample is held Amount is shown in Table 6：
Quality [Hg]f/ relative to the weight % for the initial mass for capturing block
M1 8.6
M2 6.8
M3 0
M4 1.5
M5 0
Table 6.
These examples show that using the capture block of the present invention higher mercury adsorption capacity can be obtained.
Embodiment H:In capture block M in humid medium2On mercury adsorption test
About 30 g liquid mercury bead is initially poured into glass pot, crucible is then put into reactor R1Bottom.Also The beaker for filling water is put into reactor R1Bottom.Make quality mmCapture block M of the invention2It is deposited on volume V2 = 1 L cylindrical glass reactor R2In, then by reactor R2Introduce reactor R1It is internal.
By reactor R1Regulation is introduced into the heating chamber of T=70 DEG C 1 week.
Then capture block is analyzed by X-ray diffraction analysis.Fig. 3 shows the difraction spectrum of measurement.Radiation angle " 2- θ " Represented along abscissa；The intensity " Lin " of diffraction ray represents on the vertical scale.The part for having black triangle top corresponds to The signal of metacinnabarite (HgS).Especially peak is observed at angle 26.5,30.5,43.5 and 51.5；They mean to understand Draw a conclusion on ground：In the presence of the crystalline phase of the metacinnabarite (HgS) obtained by element mercury and the reaction of Salmon-Saxl being deposited on capture block.Cause This, capture block of the invention can be used for capturing the mercury contained in wet gas phase.

Claims (15)

1. the capture block for capturing mercury, described piece includes active phase deposition on porous support, and the activity is mutually comprising member Plain sulphur, the porous carrier have pore volume V0.004>0.1 mL/g, V0.004Corresponding to the size with less than 0.004 μm Hole cumulative volume, pore volume V0.002<0.002 mL/g, V0.002Corresponding to the hole of the size with less than 0.002 μm Cumulative volume, wherein porous carrier has pore volume V0.1-0.01<0.15 mL/g, V0.1-0.01Corresponding to 0.1 μm- The cumulative volume in the hole of the size in 0.01 μ m.
2. capture block according to claim 1, wherein porous carrier are made up of at least one of following oxide：Aluminum oxide, oxygen Change titanium, zirconium oxide and silica.
3. according to the capture block of claim 1 or claim 2, wherein porous carrier is made up of aluminum oxide.
4. capture block according to claim 3, wherein porous carrier have 0.3-1 cm3Total pore volume in/g range, it is described Porous carrier has 100-400 m2BET specific surface area in/g range, and the porous carrier is included with Na2O weight meters 10-5000 ppm in the range of amount sodium.
5. capture block according to claim 1, wherein porous carrier have pore volume V0.1>0.2 mL/g, V0.1Corresponding to tool There is the cumulative volume in the hole of the size less than 0.1 μm.
6. capture block according to claim 1, wherein activity mutually includes elementary sulfur Sx, x is in the range of 1-30.
7. capture block according to claim 1, its include relative to the weight of the capture block in the range of 1%-60% with member The amount of the weight meter of plain sulphur, and relative to the weight of the capture block, the amount in terms of porous carrier weight is 40%-99%'s In the range of.
8. the method for capture block according to claim 1 is prepared, wherein making sulphur deposition on porous support.
9. method according to claim 8, wherein depositing sulphur in the following manner：By making sulfur powder be contacted with carrier, or Person is by making sulfur vapor be contacted with carrier, or by making the sulphur in liquid solution be contacted with carrier, then by heating sulfur-bearing Carrier and step is dried.
10. for removing the method for the mercury included in gaseous effluent, wherein making gaseous effluent (1) and according to claim One of 1-9 capture block (2) contact.
11. method according to claim 10, wherein carrying out drying process (5) before contact to reduce the relative of gaseous effluent Humidity.
12. method according to claim 11, wherein drying process are carried out in the following manner：By means of the sieve with water-absorption Contact, by means of being contacted with the absorbent solution comprising glycol, or pass through heated gaseous effluent.
13. according to one of claim 10-12 method, wherein the contact is at a temperature in the range of -50 DEG C to 115 DEG C Under the pressure in the range of 0.1 bar of absolute pressure to 200 bars of absolute pressures, and using 50-50000 h-1In the range of when Air speed degree is carried out.
14. the relative humidity of method according to claim 10, wherein gaseous effluent is in the range of 60%-100%.
15. method according to claim 10, wherein gaseous effluent are selected from：Burning cigarette, synthesis gas, natural gas and hydrocarbon stream go out Thing.
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